Insecticidal compounds

Abstract

A compound of formula I, (I), wherein A, Q, R 1 , and R 2 , are as defined in claim 1 . Furthermore, the present invention relates to intermediates used to prepare compounds of formula (I), to methods of using them to combat and control insect, acarine, nematode and mollusc pests and to insecticidal, acaricidal, nematicidal and molluscicidal compositions comprising them.

1 . A compound of formula I 
       
         
           
           
               
               
           
         
         wherein 
         Q is —C(═S)NR 3 R 4  or —C(═NR 5 )SR 6 ; where R 3  and R 4  can independently of each other be selected from hydrogen, C 1 -C 6 alkyl (optionally substituted by aryl, aryloxy, heteroaryl or heterocyclyl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 5 alkenyl), and where R 5  and R 6  are independently selected from hydrogen, C 1 -C 6 alkyl (optionally substituted by aryl, aryloxy, heteroaryl or heterocyclyl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 5 alkenyl); 
         A is —CH 2 —CH 2 — or —CH═CH—; 
         R 1  is halogen, cyano, C 1 -C 3  alkoxy, C 3 -C 5  cycloalkyl, —C≡CR 7 ; where R 7  is hydrogen, C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl (optionally substituted by one to two substituents independently selected from halogen, methyl and C 1 -C 2 haloalkyl), tri(C 1 -C 2 )alkylsilyl; and 
         R 2  is hydrogen, formyl, cyano, hydroxy, NH 2 , C 1 -C 6 alkyl (optionally substituted by aryl, aryloxy, heteroaryl or heterocyclyl, which themselves can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 5 alkenyl), C 1 -C 6 cyanoalkyl, C 1 -C 6 alkoxy(C 1 -C 6 )alkyl, C 1 -C 4 alkoxy(C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl, C 1 -C 6 alkylcarbonyl(C 1 -C 6 )alkyl, C 1 -C 4 alkoxyimino(C 1 -C 4 )alkyl, C 1 -C 4 haloalkoxy(C 1 -C 4 )alkyl, C 1 -C 6 alkoxycarbonyl(C 1 -C 6 )alkyl, C 1 -C 4 alkoxy(C 1 -C 4 )alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, aryloxycarbonyl(C 1 -C 6 )alkyl (wherein the aryl group can be optionally substituted by one or two substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4  haloalkyl, and C 1 -C 4 alkoxy), C 1 -C 4 alkylaminocarbonyl(C 1 -C 6 )alkyl, di(C 1 -C 4 alkyl)aminocarbonyl(C 1 -C 6 )alkyl, C 1 -C 4 haloalkylaminocarbonyl(C 1 -C 6 )alkyl, di(C 1 -C 4 haloalkyl)aminocarbonyl-C 1 -C 6 alkyl, C 1 -C 2 alkoxy(C 2 -C 4 )alkylaminocarbonyl(C 1 -C 4 )alkyl, C 2 -C 6 alkenyloxycarbonyl(C 1 -C 6 )alkyl, C 3 -C 6 alkynyloxycarbonyl(C 1 -C 6 )alkyl, (R 9 O) 2 (O═)P(C 1 -C 6 )alkyl where R 8  is hydrogen, C 1 -C 4 alkyl or benzyl, C 3 -C 7 cycloalkyl (optionally substituted by one to three substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy and, additionally, one of the ring member units can optionally represent C═O or C═NR 9  where R 9  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, C 1 -C 4 alkoxy, or C 3 -C 6 cycloalkyl), C 3 -C 7 halocycloalkyl, C 3 -C 7 cycloalkenyl (optionally substituted by one or two substituents independently selected from C 1 -C 4 alkyl, and C 1 -C 4 haloalkyl, and, additionally, one of the ring member units can optionally represent C═O), C 3 -C 7 halocycloalkenyl, C 1 -C 6 alkyl-S(═O)n 1 (C 1 -C 6 )alkyl where n 1  is 0, 1 or 2, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, aryl(C 3 -C 6 )alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, aryl(C 3 -C 6 )alkynyl, C 3 -C 6 hydroxyalkynyl, C 1 -C 6 alkoxycarbonyl (optionally substituted by one to three substituents independently selected from halogen, hydroxy, cyano, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, and aryl), aryloxycarbonyl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy), C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, aminocarbonyl, C 1 -C 6 alkylaminocarbonyl, di(C 1 -C 6 )alkylaminocarbonyl, aminothiocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di(C 1 -C 6 )alkylaminothiocarbonyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 8 alkynyloxy, aryloxy (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), C 1 -C 6 alkylamino, di(C 1 -C 6 )alkylamino, C 3 -C 6 cycloalkylamino, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, aryl-S(═O)n 2  (optionally substituted by one or two substituents independently selected from halogen, nitro, and C 1 -C 4 alkyl) where n 2  is 0, 1 or 2, aryl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, and C 1 -C 4 haloalkoxy), heteroaryl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, and C 1 -C 4 haloalkoxy), heterocyclyl (optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, and C 1 -C 4 haloalkoxy, and, additionally, a ring member unit can optionally represent C═O or C═NR 10  where R 10  is hydrogen, C 1 -C 4  alkyl, C 1 -C 4  haloalkyl, C 1 -C 4  cyanoalkyl, C 1 -C 4  alkoxy, or C 3 -C 6  cycloalkyl), (C 1 -C 6 alkylthio)carbonyl, (C 1 -C 6 alkylthio)thiocarbonyl, C 1 -C 6 alkyl-S(═O)n 3 (═NR 11 )—C 1 -C 4 alkyl wherein R 11  is hydrogen, cyano, nitro, C 1 -C 4 alkyl and n 3  is 0 or 1; or an agrochemically acceptable salt, N-oxide or isomer thereof. 
       
     
     
         2 . A compound according to  claim 1  wherein Q is —C(═S)NR 3 R 4  or —C(═NR 5 )SR 6 ; where R 3  and R 4  are each independently selected from hydrogen, C 1 -C 6 alkyl (optionally substituted by phenyl which can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), and C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 6 alkenyl); and R 5  and R 6  are each independently selected from hydrogen, C 1 -C 6 alkyl (optionally substituted by phenyl which can be optionally substituted by one to three substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxy), and C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 5 alkenyl). 
     
     
         3 . A compound according to  claim 1  wherein R 1  is halogen, cyano, C 1 -C 3 alkoxy, C 3 -C 5 cycloalkyl, or —C≡CR 7  where R 7  is hydrogen, C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl (which is optionally substituted by one to two substituents independently selected from halogen, methyl and C 1 -C 2 haloalkyl), or tri(C 1 -C 2 )alkylsilyl. 
     
     
         4 . A compound according to  claim 1  wherein R 2  is hydrogen, C 1 -C 6 alkyl [optionally substituted by phenyl, phenoxy, heteroaryl (wherein the heteroaryl is pyrimidinyl, pyrazolyl, imidazolyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, or thiadiazolyl) or heterocyclyl (wherein heterocyclyl is oxetanyl, thietanyl, tetrahydrofuranyl, [1,3]dioxolanyl, 1-oxo-thietanyl or 1,1-dioxo-thietanyl), which themselves can be optionally substituted by one to two substituents independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and C 1 -C 4 alkoxyl, C 1 -C 6 haloalkyl (optionally substituted by one to two substituents independently selected from hydroxy, C 1 -C 4 -alkoxy, tri(C 1 -C 4 alkyl)silyloxy, C 1 -C 2 alkylcarbonyloxy, and C 3 -C 5 alkenyl), C 1 -C 6 cyanoalkyl, C 1 -C 6 alkoxy(C 1 -C 6 )alkyl, C 1 -C 4 alkoxy(C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl, C 1 -C 6 alkylcarbonyl(C 1 -C 6 )alkyl, C 1 -C 6 alkoxycarbonyl(C 1 -C 6 )alkyl, hydroxycarbonyl(C 1 -C 6 )alkyl, C 1 -C 4 alkylaminocarbonyl(C 1 -C 6 )alkyl, C 1 -C 4 haloalkylaminocarbonyl(C 1 -C 6 )alkyl, C 2 -C 6 alkenyloxycarbonyl(C 1 -C 6 )alkyl, C 3 -C 6 cycloalkyl (optionally substituted by one to two substituents independently selected from C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, and C 1 -C 2 alkoxy and, additionally, wherein one of the ring member units can optionally represent C═O), C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkenyl (wherein one of the ring member units can optionally represent C═O), C 1 -C 6 alkyl-S(═O)n 1 (C 1 -C 6 )alkyl where n 1  is 0, 1 or 2, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkoxycarbonyl (optionally substituted by halogen, hydroxy, cyano, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, or phenyl), C 3 -C 6 alkenyloxycarbonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, phenyl-S(═O)n 2  (optionally substituted by one or two substituents independently selected from halogen, nitro, and C 1 -C 4 alkyl) where n 2  is 2, heterocyclyl (wherein the heterocyclyl is oxetanyl, thietanyl, tetrahydrofuranyl, tetrahydropyranyl, [1,3]dioxolanyl, 1-oxo-thietanyl or 1,1-dioxo-thietanyl, and wherein the heterocyclyl can be optionally substituted by one to three substituents independently selected from halogen, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, and C 1 -C 2 haloalkoxy, and, additionally, wherein a ring member unit can optionally represent C═O), or C 1 -C 4 alkyl-S(═O)n 3 (═NR 17 )—C 1 -C 4 alkyl wherein R 17  is hydrogen, cyano, nitro, C 1 -C 4 alkyl and n 3  is 0 or 1. 
     
     
         5 . A compound according to  claim 1  wherein Q is —C(═S)NR 3 R 4  or —C(═NR 5 )SR 6 ; where R 3  and R 4  are each independently hydrogen or C 1 -C 6 alkyl; R 5  is hydrogen; and R 6  is C 1 -C 6 alkyl. 
     
     
         6 . A compound according to  claim 1  wherein R 1  is chloro, bromo, cyano, or —C≡CR 7  where R 7  is hydrogen. 
     
     
         7 . A compound according to  claim 1  wherein R 2  is hydrogen, C 1 -C 4 alkyl, C 1 -C 6 haloalkyl, C 1 -C 4 cyanoalkyl, C 1 -C 4 alkoxy(C 1 -C 4 )alkyl, C 1 -C 2 alkylcarbonyl(C 1 -C 2 )alkyl, C 1 -C 3 alkoxycarbonyl(C 1 -C 3 )alkyl, hydroxycarbonyl(C 1 -C 3 )alkyl, C 1 -C 3 alkylaminocarbonyl(C 1 -C 3 )alkyl, C 1 -C 3 haloalkylaminocarbonyl(C 1 -C 3 )alkyl, C 2 -C 4 alkenyloxycarbonyl(C 1 -C 3 )alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkyl-S(═O)n 1 (C 1 -C 4 )alkyl where n 1  is 0, 1 or 2, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, or heterocyclyl (wherein the heterocyclyl is oxetanyl, thietanyl, tetrahydropyranyl, 1-oxo-thietanyl or 1,1-dioxo-thietanyl). 
     
     
         8 . A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in  claim 1 . 
     
     
         9 . A method according to  claim 8  wherein the pests are insects are from the order hemiptera, which insects are resistant to a neonicotinoid insecticide. 
     
     
         10 . A method according to  claim 8  wherein undesired pests are controlled but beneficial arthropods are not affected. 
     
     
         11 . A method according to  claim 8  wherein the method comprises applying a compound of formula (I) and one or more beneficial arthropods. 
     
     
         12 . A method according to  claim 10  wherein the beneficial arthropods are one or more beneficial insects or predatory mites selected from  Orius insidiosus, Orius laevigatus, Orius majusculus, Coccinella septempunctata, Adalia bipunctata, Amblydromalus limonicus, Amblyseius andersoni, Amblyseius barkeri, Amblyseius califomicus, Amblyseius cucumeris, Amblyseius montdorensis, Amblyseius swirskii, Phytoseiulus persimilis, Syrphus  spp., and  Phytoseiulus persimilis.    
     
     
         13 . A method according to  claim 8  wherein the insects are from the Aleyrodidae family or the Aphididae family. 
     
     
         14 . An insecticidal acaricidal, nematicidal or molluscicidal composition comprising an insecticidally acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in  claim 1 .